WO2019050185A1 - Cellule solaire et son procédé de fabrication - Google Patents

Cellule solaire et son procédé de fabrication Download PDF

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Publication number
WO2019050185A1
WO2019050185A1 PCT/KR2018/009356 KR2018009356W WO2019050185A1 WO 2019050185 A1 WO2019050185 A1 WO 2019050185A1 KR 2018009356 W KR2018009356 W KR 2018009356W WO 2019050185 A1 WO2019050185 A1 WO 2019050185A1
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layer
solar cell
metal compound
conductivity type
silicon substrate
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Korean (ko)
Inventor
이기원
권정효
심구환
양영성
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LG Electronics Inc
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LG Electronics Inc
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Priority claimed from KR1020170113463A external-priority patent/KR102541127B1/ko
Priority claimed from KR1020170134041A external-priority patent/KR102600452B1/ko
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Publication of WO2019050185A1 publication Critical patent/WO2019050185A1/fr
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/161—Photovoltaic cells having only PN heterojunction potential barriers comprising multiple PN heterojunctions, e.g. tandem cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/30—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells
    • H10F19/31—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells having multiple laterally adjacent thin-film photovoltaic cells deposited on the same substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • H10F77/164—Polycrystalline semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • H10F77/166—Amorphous semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solar cell which suppresses leakage current by a tunnel junction structure and has excellent temperature characteristics and photoelectric conversion efficiency, a tandem solar cell which maximizes current efficiency through current matching between an upper solar cell and a lower solar cell, And a method of manufacturing a solar cell capable of simultaneously depositing a unit layer of an upper solar cell during the manufacturing process of the solar cell.
  • Crystalline silicon (c-Si) solar cells are a typical single junction solar cell and are now widely used as commercial solar cells.
  • FIG. 1 schematically shows a cross section of a typical two-terminal tandem solar cell among the tandem solar cells.
  • a tandem solar cell includes a single junction solar cell including an absorption layer having a relatively large band gap and a single junction solar cell including an absorption layer having a relatively small band gap, Junction layer " or " inter-layer ").
  • a perovskite / crystalline silicon tandem solar cell using a single junction solar cell including an absorbing layer having a relatively large band gap as a perovskite solar cell achieves a photoelectric efficiency as high as 30% or more I can get a lot of attention.
  • a crystalline silicon solar cell used as a lower solar cell of a conventional tandem solar cell is mainly used with a hetero-junction with intrinsic thin layer silicon solar cell known to have high photoelectric conversion efficiency.
  • the heterojunction silicon solar cell comprises a very thin layer of n-type or p-type conductivity type amorphous silicon layer (na-Si or pa-Si) and an intrinsic amorphous silicon layer (ia-Si) on the front / rear surface of a single- .
  • This heterojunction structure is known to have a high photoelectric conversion efficiency due to a high band gap of the a-Si layer and a good interfacial property of the a-Si layer and the crystalline Si substrate.
  • the absorption of solar light is excessively caused by the doping layer, that is, the n-type or p-type conductivity type amorphous silicon layer (na-Si or pa-Si) There is a problem that the transmittance is lowered.
  • the heterojunction silicon solar cell has a short circuit current density (Jsc) lower than other silicon solar cells. It is known that the low short circuit current density is due not only to limited photocurrent collection due to the low light transmittance of the heterojunction silicon solar cell but also because of the low internal quantum efficiency in the amorphous silicon layer.
  • the present invention aims to maximize the efficiency of a single solar cell and a tandem solar cell by improving the light transmittance by applying a tunnel junction structure to a silicon solar cell in a single solar cell and a tandem solar cell.
  • the solar cell of the present invention can be applied to a lower surface of a silicon solar cell by applying a heterojunction structure as well as a tunnel junction, Of the solar cell to reach and absorb in the light absorbing layer of the silicon solar cell, thereby maximizing the efficiency of the solar cell and increasing the degree of process freedom.
  • the present invention aims to maximize the efficiency of the tandem solar cell by designing the material of the unit layer of the lower solar cell and the upper solar cell in the tandem solar cell and matching the current between the solar cells.
  • the method of manufacturing a tandem solar cell according to the present invention is to provide a method of manufacturing a tandem solar cell in which productivity is improved by applying a process of simultaneously depositing a unit layer of a top solar cell during a process of manufacturing a bottom solar cell .
  • the first solar cell comprises: a crystalline silicon substrate; A first conductive type layer formed on the first surface of the crystalline silicon substrate and made of silicon doped with a dopant; A tunnel layer located on a second surface of the crystalline silicon substrate; And a second conductivity type layer made of a metal compound located on the tunnel layer.
  • a tunnel junction structure to a silicon solar cell, a crystalline silicon substrate; A first conductive type layer formed on the first surface of the crystalline silicon substrate and made of silicon doped with a dopant; A tunnel layer located on a second surface of the crystalline silicon substrate; And a second conductivity type layer made of a metal compound located on the tunnel layer.
  • the material of the unit layer of the lower solar cell and the upper solar cell can be designed to maximize the efficiency of the tandem solar cell through current matching between the solar cells.
  • a second solar cell disposed on the first solar cell wherein the first solar cell comprises: a crystalline silicon substrate; A first conductive type layer located on a first surface of the crystalline silicon substrate and containing a first metal compound; A second conductive type layer located on a second surface of the crystalline silicon substrate and containing a second metal compound;
  • the solar cell of the present invention can be provided.
  • the solar cell further comprises an intermediate layer between the first solar cell and the second solar cell.
  • the tunnel layer or heterojunction layer located on the first surface further comprises a tunnel layer or a heterojunction layer located on the first surface of the crystalline silicon substrate, wherein the tunnel layer or the heterojunction layer located on the first surface is a silicon oxide layer or an intrinsic amorphous silicon layer
  • the solar cell of the present invention can be provided.
  • the first conductive type layer is any one of amorphous silicon, microcrystalline silicon, and polycrystalline silicon.
  • the thickness of the tunnel layer located on the second surface of the crystalline silicon substrate is 1 to 2 nm.
  • the thickness of the second conductivity type layer located on the tunnel layer is 1 to 100 nm.
  • the metal compound is one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 .
  • the metal compound is one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, and VO x .
  • the second solar cell has a first conductivity type charge transporting layer; A perovskite absorption layer located on the first conductivity type charge transporting layer; And a second conductivity type charge transporting layer disposed on the perovskite absorption layer.
  • the first conductivity type charge transporting layer is one or more selected from the group consisting of an electron conductive organic layer, an electron conductive inorganic layer, or silicon (Si) layer;
  • the second conductivity type charge transporting layer is one or more selected from a layer including a hole-transporting organic compound layer, a hole-conducting metal oxide, or silicon (Si).
  • the first conductivity type charge transporting layer may be one or more selected from the group consisting of a hole transporting organic layer, a hole transporting metal oxide or a silicon (Si) layer; And one or more selected from the layers including the electron conductive organic layer, the electron conductive inorganic layer, and the silicon (Si) layer.
  • the second solar cell has a first conductivity type charge transporting layer; A perovskite absorption layer located on the first conductivity type charge transporting layer; And a second conductivity type charge transporting layer disposed on the perovskite absorption layer.
  • the first conductive type charge transport layer may include first metal compounds of the first conductive type layer.
  • the first metal compound is one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 ;
  • the second metal compound may be one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, and VO x .
  • the second conductive type charge transporting layer may be formed of at least one selected from the group consisting of Spiro-OMeTAD, polyaniline, polypyrrole, polythiophene, poly-3,4-ethylene dioxythiophene-polystyrene sulfonate (PEDOT- Phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), polyaniline-camphorsulfonic acid (PANI-CSA), pentacene, coumarin 6, 3- (2-benzothiazolyl) -7 - (diethylamino) coumarin) can be provided.
  • Spiro-OMeTAD polyaniline
  • polypyrrole polythiophene
  • poly-3,4-ethylene dioxythiophene-polystyrene sulfonate PEDOT- Phenyl) (2,4,6-trimethylphenyl) amine]
  • PANI-CSA polyaniline-camphorsulfonic acid
  • the first metal compound is one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, and VO x ;
  • the second metal compound may be one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 .
  • the second conductive type charge transport layer is selected from among fullerene (C 60 ), PCBM, P 3 HT, polybenzimidazole (PBI), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), and tetraurortetracyanoquinodimethane
  • fullerene C 60
  • PCBM PCBM
  • P 3 HT polybenzimidazole
  • PBI polybenzimidazole
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • tetraurortetracyanoquinodimethane One or two or more solar cells may be provided.
  • the thickness of the first conductivity type layer, the second conductivity type layer, the first conductivity type charge transporting layer, and the second conductivity type charge transporting layer may be 1 to 100 nm.
  • productivity can be improved by applying a process of simultaneously depositing some unit layers of the upper solar cell during the manufacturing process of the lower solar cell, a second metal compound is formed on the second surface on the crystalline silicon substrate Forming a second conductive type layer including the second conductive type layer; Forming an intermediate layer on the second surface; and forming a first metal compound layer having a first conductivity type on the first surface and the second surface on the crystalline silicon substrate.
  • a method of manufacturing a battery can be provided.
  • the step of forming the second conductive type layer containing the second metal compound on the second surface on the crystalline silicon substrate comprises the steps of: forming the second metal compound on the first and second surfaces of the crystalline silicon substrate, At the same time; And removing the layer including the second metal compound formed on the first surface of the substrate.
  • the step of forming a first metal compound layer having a first conductivity type on the first surface and the second surface on the crystalline silicon substrate may include forming a first conductive type semiconductor layer on the first and second surfaces, And the first metal compound layer having the first metal compound layer having the first metal compound layer are formed at the same time.
  • the step of forming the first metal compound layer having the first conductivity type on the first surface and the second surface on the crystalline silicon substrate includes the steps of: injecting a metal source; Purging with a gas comprising N 2 ; O 3 , N 2 O, O 2 , O 2 plasma, and radical oxidation; And purging the gas with a gas containing N 2 .
  • a step of forming a transparent electrode layer on the first metal compound layer on the first surface a step of forming a transparent electrode layer on the first metal compound layer on the first surface; Forming a perovskite absorption layer on the first metal compound layer on the second surface; And a step of forming a charge transport layer of a second conductivity type on the perovskite absorption layer.
  • the second metal compound is one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, and VO x ;
  • the first metal compound is one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 , MgO / TiO 2 , and the like.
  • the second conductive type charge transporting layer may be formed of at least one selected from the group consisting of Spiro-OMeTAD, polyaniline, polypyrrole, polythiophene, poly-3,4-ethylene dioxythiophene-polystyrene sulfonate (PEDOT- Phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), polyaniline-camphorsulfonic acid (PANI-CSA), pentacene, coumarin 6, 3- (2-benzothiazolyl) -7 - (diethylamino) coumarin).
  • PANI-CSA polyaniline-camphorsulfonic acid
  • pentacene coumarin 6, 3- (2-benzothiazolyl) -7 - (diethylamino) coumarin.
  • the second metal compound is one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 ;
  • the first metal compound is one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, and VO x .
  • the second conductive type charge transporting layer may be formed of one or two selected from among fullerene (C60), PCBM, P3HT, polybenzimidazole (PBI), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), and tetraurorotetracyanoquinodimethane Or more of the total mass of the solar cell can be provided.
  • a solar cell according to an embodiment (first embodiment) of the present invention introduces a tunnel junction structure in a crystalline silicon solar cell used as a lower solar cell in a single solar cell or a tandem solar cell, thereby suppressing absorption of sunlight, So that photoelectric conversion efficiency can be achieved.
  • the solar cell of the embodiment of the present invention can prevent the leakage current by forming the passivation barrier layer through the application of the tunnel structure, so that the current is collected outside the solar cell with little loss, and the photoelectric conversion efficiency can be improved.
  • the solar cell of one embodiment of the present invention not only can enhance the passivation function at the interface by forming the second conductivity type layer together with the tunnel silicon oxide on the second surface of the silicon solar cell,
  • the necessary doped silicon layer can be excluded and the short circuit current density (Jsc) can be increased.
  • the solar cell of one embodiment of the present invention can be fabricated by applying a conventional hetero-junction structure to the first surface of the silicon solar cell in addition to the tunnel junction structure, It is possible to maximize the efficiency of the tandem solar cell by allowing the sunlight of a long wavelength to reach all of the light absorption layer of the lower silicon solar cell.
  • the solar cell of another embodiment (second embodiment) of the present invention is a solar cell in which a first metal compound layer and a second metal compound layer in a crystalline silicon solar cell are made of a material containing a metal compound, Si) layer and have a high current density.
  • the solar cell according to the second embodiment of the present invention uses a crystalline silicon solar cell having a high current density as a lower solar cell of a tandem solar cell, so that the current of the tandem solar cell The effect of maximizing the efficiency can be obtained.
  • the metal compound layer in the upper solar cell can be simultaneously deposited on both sides .
  • an ALD (atomic layer deposition) process is used to form the first metal compound layer in the lower solar cell and the first conductive type charge transfer layer of the upper solar cell, Can be deposited simultaneously on both sides.
  • the productivity is dramatically improved by simplifying the manufacturing process.
  • the integration or simplification of the steps of fabricating the respective constituent layers of the solar cell not only reduces the amount of expensive deposition equipment, but also omits the unit process, thereby reducing the time (lead time) and The total process time (tact time) can be reduced.
  • the solar cell manufacturing method of the present invention can omit a part of the deposition process having very sensitive characteristics, thereby greatly improving the stability of the manufacturing process of the tandem solar cell.
  • FIG. 1 is a schematic diagram schematically showing a general tandem solar cell.
  • FIG. 2 is a cross-sectional view showing a tandem solar cell according to an embodiment (first embodiment) of the present invention.
  • FIG 3 is a cross-sectional view showing a tandem solar cell according to another embodiment (second embodiment) of the present invention.
  • FIGS. 4 and 5 are cross-sectional views illustrating a method of manufacturing a tandem solar cell according to an embodiment of the present invention.
  • FIG. 6 is a view showing a gas flow step in the ALD (atomic layer deposition) method used in the present invention.
  • FIG. 7 to 14 are cross-sectional views illustrating a method of manufacturing a tandem solar cell according to an embodiment of the present invention.
  • the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the components from other components, and the terms do not limit the nature, order, order, or number of the components.
  • FIG 2 is a cross-sectional view showing a tandem solar cell according to one embodiment (first embodiment) of the present invention.
  • FIG. 2 specifically shows a second solar cell 120 including an absorbing layer having a relatively large band gap and a first solar cell 110 including an absorbing layer having a relatively small band gap, Terminal tandem solar cell 100 directly tunnel-bonded via a " tunnel junction layer ", " junction layer “, and " inter-layer "
  • the first solar cell 110 absorbs light in the long wavelength region and generates electricity, thereby moving the threshold wavelength toward the longer wavelength side.
  • the wavelength band absorbed by the entire solar cell can be widened .
  • the tandem solar cell 100 includes a first solar cell 110 and a second solar cell 120.
  • the first solar cell may be a silicon solar cell
  • the second solar cell on the first solar cell may be a perovskite solar cell, but the present invention is not limited thereto.
  • the second solar cell of the present invention can be applied to any solar cell having a bandgap larger than the bandgap of the first solar cell while being located on the first solar cell.
  • the solar cell according to the present invention is a single solar cell
  • the single solar cell in the present invention is a silicon solar cell which is one specific embodiment of the first solar cell 110.
  • tandem solar cell according to the present invention includes all components of the single solar cell of the present invention as it is, so that the tandem solar cell of the present invention will be described below.
  • the solar cell 100 as one embodiment (first embodiment) of the present invention comprises a first solar cell 110; And a second solar cell (120) located on the first solar cell and having a bandgap larger than a bandgap of the first solar cell, wherein the first solar cell (110) comprises a crystalline silicon substrate ); A tunnel layer (112-1) located on a second surface of the crystalline silicon substrate; A second conductive type layer 112-2 located on the tunnel layer 112-1; A tunnel layer or heterojunction layer 113-1 located on the first surface of the crystalline silicon substrate; A doped first conductive type layer 113-2 located on the tunnel layer or the heterojunction layer 113-1 on the first surface; And a first electrode 140 on the first conductive type layer 113-2.
  • the intermediate layer 114 may be inserted as needed.
  • the intermediate layer 114 may be formed of a transparent conductive oxide, a carbonaceous conductive material, or a metallic material, such as a transparent conductive oxide, or a carbonaceous conductive material, so that light of a long wavelength transmitted through the second solar cell 120 can be incident on the lower first solar cell 110, . ≪ / RTI >
  • the intermediate layer 114 may be doped with an n-type or p-type material.
  • ITO Indium Tin Oxide
  • IWO Indium Tin Oxide
  • ZITO Zinc Indium Tin Oxide
  • ZIO Zinc Indium Oxide
  • GTO Gallium Indium Tin Oxide
  • GZO Gallium Zinc Oxide
  • AZO Aluminum-doped Zinc Oxide
  • FTO Fluorine Tin Oxide
  • ZnO Zinc Oxide
  • Graphene or carbon nanotubes can be used as a carbonaceous conductive material and a metal thin film of a multilayered structure such as metal nanowire or Au / Ag / Cu / Mg / Mo / Ti can be used as a metallic material.
  • the first solar cell 110 in the tandem solar cell 100 of the present invention is a crystalline silicon solar cell
  • the first solar cell 110 also forms a texture (at least on the first surface) .
  • First tunnel layer positioned on the first surface and / or the second surface of the crystalline silicon substrate of the present invention to form a tunnel junction (junction) are composed of a tunnel silicon oxide represented by SiO 2 Loses.
  • the tunnel silicon oxide acts as a kind of barrier to electrons and holes to prevent minority carriers from passing through and is accumulated in a portion adjacent to the tunnel layers 112-1 and 113-1, Only the majority carriers having the above energy can pass through the tunnel silicon oxides 112-1 and 113-1, respectively. At this time, a plurality of carriers having an energy of a certain level or higher can easily pass through the tunnel layers 112-1 and 113-1 by the tunneling effect.
  • the thickness of the tunnel layers 112-1 and 113-1 made of the tunnel silicon oxide is preferably 1 to 2 nm so that the tunneling effect can be sufficiently realized.
  • the tunnel silicon oxide becomes difficult to perform the role of blocking the minority carriers due to the excessively thin thickness.
  • the thickness of the tunneling silicon oxide is greater than 2 nm, the excessively thick thickness prevents the majority carriers from passing through the tunneling silicon oxide. In other words, the tunnel silicon oxide can not perform the function of tunneling.
  • tunnel junctions can be formed of various materials.
  • intrinsic amorphous silicon semiconductors can also form tunnel junctions.
  • the tunnel junction film and the semiconductor substrate 110 include the same semiconductor material and have similar characteristics, the surface characteristics of the semiconductor substrate 110 can be improved more effectively. As a result, the passivation characteristic can be greatly improved.
  • silicon oxide having high light transmittance is used in the present invention.
  • silicon oxide represented by SiO 2 is more preferable as the tunnel layer.
  • a second conductive type layer 112-2 is formed on the tunnel silicon oxide 112-1 located on the second surface.
  • the second conductive type layer 112-2 in the present invention may have a conductive type which is the same as or opposite to the conductive type of the crystalline silicon substrate 111.
  • the second conductivity type layer 112-2 may be a second conductivity type layer which can serve as a p-type hole transport layer.
  • the second conductivity type layer 112-2 in the present invention becomes a second conductivity type layer which can serve as an n-type electron transport layer.
  • the second conductivity type layer 112-2 performs the same function as the emitter. At this time, if the second surface is the sunlight incident surface and the first surface is the opposite surface, the second conductivity type layer 112-2 becomes the front emitter layer.
  • the second conductivity type layer 112-2 and the crystalline silicon substrate 111 may have the same conductivity type.
  • the second conductivity type layer 112-2 has the same role as the whole layer .
  • the second surface is the sunlight incident surface and the first surface is the opposite surface, the second conductivity type layer 112-2 becomes the whole front surface layer.
  • the metal compound that can act as the p-type metal compound layer may be one or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O and VO x .
  • the metal compounds selectively perform the function of transporting or transporting holes.
  • the oxide which can act as the n-type metal compound layer may be one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 . All of these metal compounds optionally carry the function of transport or transfer of electrons.
  • the thickness of the second conductivity type layer 112-2 located on the second surface of the crystalline silicon substrate in the present invention is preferably 1 to 100 nm.
  • the thickness of the second conductivity type layer 112-2 is thicker than 100 nm and the second conductivity type layer 112-2 acts as an emitter layer, the amount of the electron-holes that are recombined and disappear is increased, As the quantum efficiency decreases, the current decreases.
  • the second conductivity type layer 112-2 acts as a whole layer, the electric field is reduced and the open voltage Voc tends to decrease.
  • the thickness of the second conductive type layer 112-2 is thinner than 1 nm, the electric field is reduced due to the thickness of the excessively thin second conductive type layer 112-2, and the open voltage Voc is decreased, There is a problem that it is difficult to secure.
  • the light transmittance in the functional layer is increased compared to the conventional hetero-junction structure, It is possible to suppress the leakage current caused by the leakage current.
  • the passivation function at the interface is enhanced but also the doping is not required to be further performed, and as a result, the light absorption is reduced and the short circuit current density Js can be increased.
  • the first conductive type layer 113-2 is located on the tunneling layer or the heterojunction layer 113-1 located on the first surface of the crystalline silicon substrate 111.
  • the tunnel layer 113-1 is located on the first surface of the crystalline silicon substrate 111, as described above, the tunnel layer 113-1 on the first surface is electrically connected to the tunnel layer 112- 1). ≪ / RTI > At this time, on the tunnel layer 113-1 on the first surface, a first conductive type layer 113-2 made of a metal oxide such as a second conductive type layer 112-2 and having opposite conductivity types may be located have.
  • the heterojunction layer 113-1 is disposed on the first surface of the crystalline silicon substrate 111, as described above, the heterojunction layer 113-1 on the first surface is formed of the intrinsic amorphous silicon layer ia -Si: H).
  • the amorphous silicon layer of the present invention has a large energy band gap of about 0.6 to 0.7 eV compared to a crystalline silicon layer having an energy band gap of about 1.1 eV, and furthermore, the amorphous silicon layer can be formed very thin during the deposition process.
  • the advantage of such an amorphous silicon layer is that the light absorption loss in the short wavelength region can be minimized and the light utilization factor can be increased and the high open circuit voltage and field effect can be obtained.
  • the intrinsic amorphous silicon layer i-a-Si: H
  • the recombination of the surface of the silicon substrate can be effectively reduced.
  • a hydrogenated intrinsic amorphous silicon layer i-a-Si: H
  • i-a-Si: H hydrogenated intrinsic amorphous silicon layer
  • Hydrogen can enter the amorphous silicon by hydrogenation reaction and reduce the dangling bond of the amorphous silicon and the localized energy state in the energy bandgap.
  • the subsequent process temperature is limited to 250 ⁇ or less, and more preferably 200 ⁇ or less.
  • the process temperature is higher than 200 ° C, the hydrogen bonds inside the amorphous silicon are destroyed.
  • the first conductivity type layer 113-2 is located on the hetero junction layer 113-1 made of the intrinsic amorphous silicon layer (ia-Si: H), and the first conductivity type layer 113-2 is amorphous And may include at least one of silicon (a-Si), micro-crystalline, poly-silicone, amorphous silicon oxide (a-SiOx), and amorphous silicon carbide (a-SiCx).
  • the amorphous silicon (a-Si), micro-crystalline, polycrystalline silicon, amorphous silicon oxide (a-SiOx), amorphous silicon carbide a-SiCx) may be doped with an n-type or p-type dopant.
  • the p-type dopant include Group 3 elements such as boron (B), aluminum (Al), gallium (Ga), and indium (In).
  • the n-type dopant include phosphorus (P), arsenic (Bi), antimony (Sb), and the like.
  • the present invention is not limited thereto, and various dopants can be used.
  • the conductivity type of the first conductivity type layer 113-2 is determined according to the conductivity type of the crystalline silicon substrate 111 and the second conductivity type layer 112-2. More specifically, the conductivity type of the first conductivity type layer 113-2 is opposite to that of the second conductivity type type layer 112-2.
  • the first conductivity type layer 113-2 has a p-type
  • the mold layer 113-2 functions as an emitter layer.
  • the crystalline silicon substrate 111 is n-type and the second conductivity type layer 112-2 is p-type which is the opposite type to the substrate
  • the first conductivity type layer 113-2 has n-type
  • the mold layer 113-2 functions as a whole layer.
  • the crystalline silicon substrate 111 has the n-type conductivity
  • the second conductivity type layer 112-2 is the entire layer
  • the first conductivity type layer 113-2 is the emitter layer Is more preferable.
  • the lifetime of a charge carrier is generally long in an n-type substrate, and furthermore, the doping of boron (B), which is a typical p-type dopant, is relatively high temperature process, In order to prevent the deterioration of the film.
  • B boron
  • the thickness of the emitter layer can be freely increased and the concentration of doping can be freely increased so as to form an optimum pn junction.
  • the second conductivity type layer 112-2 and the first conductivity type layer 113-2 of the present invention are not necessarily limited thereto.
  • a polycrystalline silicon layer of homojunction may be used as the first conductivity type layer 113-2 in the present invention.
  • an allotmentally bonded crystalline silicon layer in which an impurity having a conductivity type different from that of the second conductivity type layer 112-2 is used as the doping layer may be located.
  • the tunnel layer 113-1 used as the passivation layer and the tunnel layer may not be included if necessary.
  • the first electrode 140 is positioned.
  • the first electrode 140 selectively includes a transparent electrode layer 115 positioned on the rear surface of the first conductive type layer 113-2.
  • a transparent conductive oxide such as ITO (Indium Tin Oxide), ICO (Indium Cerium Oxide), ZINT (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide)
  • a grid electrode 116 is positioned thereon.
  • the grid electrode 116 may be positioned directly on the first conductivity type layer 113-2 without forming the transparent electrode layer 115.
  • the first conductive type layer 113-2 has relatively low carrier mobility for collecting carriers through the metal grid, it is preferable to form the transparent electrode layer 115 first.
  • the thickness of the transparent electrode layer 115 in the first solar cell may be different from that of the transparent electrode layer 125 in the second solar cell to be described later.
  • the transparent electrode layer performs a function of absorbing sunlight and a function of transporting electric charge without electrical loss.
  • the transparent electrode layer 115 in the first solar cell is more important in the function of transferring the electric charge.
  • the transparent electrode layer 125 in the second solar cell has a very important function of absorbing solar light of short wavelength.
  • the transparent electrode layer 115 in the first solar cell is relatively thicker than the transparent electrode layer 125 of the second solar cell for better electric transport.
  • the transparent electrode layer 125 in the second solar cell is preferably formed to be thinner than the transparent electrode layer 115 for better light transmittance.
  • the paste for the grid electrode 116 of the first electrode 140 in the present invention may include glass frit or may not include glass frit.
  • the grid electrode 116 of the first electrode 140 may be manufactured by selectively applying a first electrode paste that does not include glass frit, followed by low-temperature firing at the formation temperature of the first electrode 140.
  • the first electrode paste may include metal particles and an organic material that is a binder for low-temperature firing, and the first electrode paste does not include glass frit.
  • the formation temperature of the grid electrode 116 of the first electrode 140 may be 250 ° C or less, more specifically, 100-200 ° C.
  • the first electrode 140 can be formed at the same step as the second electrode 130, which will be described later.
  • the grid electrode 116 of the first electrode 140 may be fabricated by selectively applying a paste containing the glass frit, followed by high-temperature firing at the formation temperature of the first electrode 140.
  • the paste for the grid electrode 116 of the first electrode 140 includes not only organic matters such as metal particles and binders but also inorganic particles that require a high temperature for melting such as glass frit.
  • the temperature for forming the first electrode 140 is relatively higher than the formation temperature of the second electrode 130, which will be described later, so that it is formed in a process separate from the second electrode.
  • the tandem solar cell 100 includes not only the first solar cell 110 but also the upper second solar cell 120.
  • the upper second solar cell 120 includes, for example, a first conductive type charge transport layer 121 disposed on a lower first solar cell; A perovskite absorption layer 122 located on the first conductivity type charge transport layer; A second conductivity type charge transport layer 123 located on the perovskite absorption layer 122; And a second electrode 130 disposed on the second conductive type charge transport layer 123.
  • the first conductive type charge transport layer 121 is formed of n -Type electron transporting layer and the second conductivity-type charge transporting layer 123 may be a p-type hole transporting layer.
  • the second conductivity type layer 112-2 of the first solar cell 110 is a p-type emitter layer of the opposite type to the substrate, and the first conductivity type layer 113-2 is n And functions as a whole hierarchy.
  • the first conductive type charge transport layer 121 is a p-type hole transport layer and the second conductive type charge transport layer 123 is an n-type Electron transport layer.
  • the second conductivity type layer 112-2 of the first solar cell 110 is an n-type whole layer of the same type as the substrate, the first conductivity type layer 113-2 has a p- And the like.
  • a p-type single crystal silicon substrate is also possible as the conductive type of the crystalline silicon substrate 111 of the first solar cell 110.
  • the first conductive type charge transport layer 123 and the second conductive type charge 113-2 may be formed depending on the conductivity type of the crystalline silicon substrate 111, the second conductivity type layer 112-2, and the first conductivity type layer 113-2, It is obvious that the conductivity type of the transport layer 121 is determined.
  • the electron transport layer applicable in the present invention may be formed of a layer including an electron conductive organic layer, an electron conductive inorganic material layer, or silicon (Si).
  • the electron conductive organic material may be an organic material used as an n-type semiconductor in a conventional solar cell.
  • the electron-conducting organics include fullerenes (C 60 , C 70 , C 74 , C 76 , C 78 , C 82 , C 95 ), PCBM ([6,6] -phenyl- C 61 butyric acid methyl ester (Fulleren-derivative), PBI (polybenzimidazole), PTCBI (3, 4, 6) -phenyl C70-butyric acid methyl ester, 9,10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ (tetrauorotetracyanoquinodimethane), or mixtures thereof.
  • the electron conductive inorganic material may be a metal oxide conventionally used for electron transfer in a conventional quantum dot-based solar cell or a dye-sensitized solar cell.
  • the metal oxide include Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, A material selected from one or more of V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide and SrTi oxide, or a mixture thereof or a composite thereof .
  • the electron transporting layer made of a layer containing silicon (Si) is more specifically composed of amorphous silicon (na-Si), amorphous silicon oxide (na-SiO), amorphous silicon nitride (na-SiN), amorphous silicon carbide SiC), amorphous silicon oxynitride (na-SiON), amorphous silicon carbonitride (na-SiCN), amorphous silicon germanium (na-SiGe), microcrystalline silicon (n-uc-Si) (n-uc-SiGe), microcrystalline silicon carbide (n-uc-SiC), microcrystalline silicon nitride .
  • the hole transporting layer applicable in the present invention may be formed of a layer including a hole-transporting organic compound layer, a hole-transporting metal oxide, or silicon (Si).
  • the hole-conducting organic material can be used as an organic hole-transporting material conventionally used for hole transport in a conventional dye-sensitized solar cell or an organic solar cell.
  • the electron conductive organics may be selected from the group consisting of polyaniline, polypyrrole, polythiophene, poly-3,4-ethylene dioxythiophene-polystyrene sulfonate (PEDOT- (2,4,6-trimethylphenyl) amine] (PTAA), polyaniline-camphorsulfonic acid (PANI-CSA), pentacene, coumarin 6, 3- (2-benzothiazolyl) diethylamino coumarin, zinc phthalocyanine, copper phthalocyanine, titanium oxide phthalocyanine (TiOPC), Spiro-MeOTAD (2,2 ', 7,7'-tetrakis (N, Np-dimethoxyphenylamino) -spirobifluorene), F16
  • the metal oxide includes Ni oxide, Mo oxide, and V oxide.
  • the hole transporting layer may further include a p-type dopant if necessary.
  • the hole transport layer containing silicon (Si) in the present invention may be formed of amorphous silicon (pa-Si), amorphous silicon oxide (pa-SiO), amorphous silicon nitride (pa-SiN), amorphous silicon carbide SiC), amorphous silicon oxynitride (pa-SiON), amorphous silicon carbonitride (pa-SiCN), amorphous silicon germanium (pa-SiGe), microcrystalline silicon (p-uc-SiGe), microcrystalline silicon germanium (p-uc-SiGe), microcrystalline silicon carbide .
  • the second solar cell 120 in the present invention includes a perovskite absorption layer 122 located between the first conductivity type charge transport layer 121 and the second conductivity type charge transport layer 123.
  • the perovskite absorption layer 122 in the present invention can be used for both the so-called MA (Methylamminium) -based or FA (Formamidinium) -based perovskite compounds currently in widespread use.
  • MA Metalamminium
  • FA Formamidinium
  • MAPbI 3 which is a typical perovskite compound of MA (Methylamminium) system having a band gap of about 1.55-1.6 eV
  • MA Metalamminium
  • FA Formamidinium
  • the FA-based perovskite compound has a unique advantage that it is superior in high-temperature stability to the MA-based perovskite compound. In addition, it has been confirmed that when the FA based perovskite compound is doped with Br, the band gap of the perovskite compound is increased.
  • FA 1-x Cs x PbBr y I 3-y which is an FA-based perovskite absorbing layer, has an advantage of being superior in high-temperature stability to MA and also has an advantage of producing an undesired delta (?) FA compound Can be suppressed.
  • the addition of Br can increase the bandgap of the FA-based perovskite absorption layer to a level similar to that of the existing MA-based perovskite absorption layer.
  • the band gap energy is increased to a high range, the perovskite layer having a high band gap absorbs light of a short wavelength compared to the conventional silicon solar cell, so that the thermal loss caused by the difference between the photon energy and the band gap is reduced, Voltage can be generated. As a result, the efficiency of the solar cell is increased.
  • a second conductivity type charge transport layer 123 having a conductivity type different from that of the first conductivity type charge transport layer 121 is disposed on the perovskite absorption layer 122.
  • the second electrode 130 is positioned on the second conductive type charge transport layer 123 of the present invention.
  • the second electrode 130 includes a transparent electrode layer 125 first.
  • the transparent electrode layer 125 is formed on the entire upper surface of the perovskite solar cell 120 to collect the charge generated in the perovskite solar cell 120.
  • the transparent electrode layer 125 may be implemented as a variety of transparent conductive materials. As the transparent conductive material, the same material as the transparent conductive material of the intermediate layer 114 may be used.
  • the grid electrode 126 is positioned on the transparent electrode layer 125 and disposed in a part of the transparent electrode layer 125.
  • the grid electrode 126 of the second electrode 130 may be manufactured by selectively applying a second electrode paste not including glass frit and then low-temperature firing at a first temperature.
  • the second electrode paste may include metal particles and an organic material that is a binder for low-temperature firing, and the second electrode paste does not include glass frit.
  • the second temperature may be 250 ⁇ or less, more specifically 100 to 200 ⁇ .
  • the grid electrode 116 of the first electrode 140 and the grid electrode 126 of the second electrode 130 may be simultaneously formed when the second electrode 130 is formed,
  • the second electrode 130 may be formed after the second solar cell is formed after the electrode 140 is formed. If the grid electrode 116 of the first electrode 140 and the grid electrode 126 of the second electrode 140 are formed at the same time as the first electrode 140 and the second electrode 130, Are all formed by a low-temperature baking process at 250 DEG C or less.
  • the solar cell according to the present invention can be used not only as a tandem solar cell, but also as a single solar cell.
  • the solar cell of the present invention can be used as the first solar cell 110 alone.
  • the solar cell of the present invention specifically includes a crystalline silicon substrate 111; A tunnel layer (112-1) located on a second surface of the crystalline silicon substrate; A second conductive type layer 112-2 located on the tunnel layer 112-1; A tunnel layer or heterojunction layer 113-1 located on the first surface of the crystalline silicon substrate; A doped first conductive type layer 113-2 located on the tunnel layer or the heterojunction layer 113-1 on the first surface; And a first electrode 140 on the first conductive type layer 113-2.
  • a solar cell as another embodiment includes: a first solar cell; And a second solar cell (120) located on the first solar cell (110) and having a band gap larger than a bandgap of the first solar cell, wherein the first solar cell (110) (111); A second metal compound layer 112 located on a second surface of the crystalline silicon substrate and having a second conductivity type; A first metal compound layer (113) formed on a first surface of the crystalline silicon substrate and having a first conductivity type; And a first electrode 140 disposed on the first metal compound layer 113 (FIG. 3).
  • the second metal compound layer 112 located on the second surface of the crystalline silicon substrate and having the second conductivity type may have a type opposite to that of the first conductive type crystalline silicon substrate 111.
  • the second metal compound layer 112 is a metal compound layer that can function as a p-type hole transport layer
  • the first metal compound layer 113 is an n- It is a metal compound layer that can act as a transport layer.
  • the second metal compound layer 112 is a metal compound layer which can act as an n-type electron transporting layer
  • the first metal compound layer 113 is a p- And becomes a metal compound layer which can act as a hole transport layer.
  • the second metal compound layer 112 having the second conductive type and the crystalline silicon substrate 111 may have the same type of conductive type.
  • the solar cell of the other embodiment differs only in the bonding structure of the first solar cell when compared with the solar cell of the foregoing. Therefore, only differences between the solar cell of the other embodiment (the second embodiment) and the solar cell of the first embodiment will be described below.
  • the compounds that can act as the p-type metal compound layer in the solar cell of the second embodiment include MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O, VO x Or a combination thereof.
  • the compound capable of acting as the n-type metal compound layer may be one or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 .
  • the thickness of the first metal compound layer 113 of the first conductivity type in the solar cell of the second embodiment is the same as the thickness of the second metal oxide layers 112 and 122-2 in the range of 1 to 100 nm.
  • the thickness of the first metal compound layer 113 When the thickness of the first metal compound layer 113 is 100 nm or more, the electric field is reduced and the open-circuit voltage (Voc) tends to decrease. On the other hand, when the thickness of the first metal compound layer 113 is 1 nm or less, there is a problem that it is difficult to ensure the performance of the charge accelerating function of the first metal compound layer 113.
  • the tandem solar cell 100 in the other embodiment (second embodiment) of the present invention also includes the second solar cell 120 as well as the first solar cell 110.
  • the second solar cell 120 includes, for example, a first conductive type charge transport layer 121 disposed on the first solar cell; A perovskite absorption layer 122 located on the first conductivity type charge transport layer; A second conductivity type charge transport layer 123 located on the perovskite absorption layer 122; And a second electrode 130 disposed on the second conductive type charge transport layer 123.
  • the metal compound used as the first conductivity type charge transporting layer 121 is the metal compound used in the crystal silicon solar cell 110 It can be used as it is.
  • the first conductive type charge transport layer 121 For example, the first conductive type charge transport layer 121.
  • the electron transport layer of the n-type TiO 2, ZnO, SnO 2, Nb 2 O 5, Al 2 O 3, MgO / TiO 2 from more than one or two selected A first metal compound is used.
  • the first conductive type charge transport layer 121 In this case, the hole transport layer of the p-type MoO x, NiO, WO 3, CuSCN, CuI, CuO, a second metal compound at least one or more selected from Cu 2 O, VO x Is used.
  • FIGS. 4 to 14 are cross-sectional views showing steps of a method for manufacturing a tandem solar cell according to the present invention and gas flow steps in an ALD process used in the present invention.
  • a crystalline silicon solar cell is first prepared.
  • the front surface and the rear surface of the crystalline silicon substrate 111 are planarized, and at least one of the front surface and the rear surface is textured to form a texturing pattern.
  • a flattened flat crystalline silicon substrate 111 may also be used.
  • the introduction of the texture structure of the crystalline silicon substrate 111 can be performed by any one of a wet chemical etching method, a dry chemical etching method, an electrochemical etching method, and a mechanical etching method, but is not limited thereto.
  • a wet chemical etching method a dry chemical etching method
  • an electrochemical etching method a mechanical etching method
  • at least one or more of the first and second surfaces of the crystalline silicon substrate 111 may be etched in a basic aqueous solution to introduce a texture structure.
  • an n-type silicon single crystal substrate sliced along the (100) plane and having a thickness of several tens to several hundreds of micrometers was prepared.
  • an aqueous solution containing an additive such as an organic solvent, a phosphate, a reaction modifier and / or a surfactant is used in an aqueous solution of 1 to 5 wt% of sodium hydroxide (NaOH) or potassium hydroxide (KOH) at a temperature ranging from room temperature to 150 ° C
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • the organic solvent may be 2-methyl-2,4-pentanediol, propylene glycol, 2,2,4-trimethyl-1,3-pentanediol (2, 2,4-trimethyl-1,3-pentanediol, 1,3-butanediol, 1,4-butanediol, 1,6- hexanediol, 2,2-dimethyl-1,3-propanediol, hydroquinone, 1,4-cyclohexanediol, And N-methyl proline may be used.
  • the phosphate may be at least one of K 3 PO 4 and K 2 HPO 4 .
  • the etching Through the etching, a texture having pyramidal irregularities was formed on the silicon single crystal substrate. Since the silicon single crystal has a diamond cubic structure, the ⁇ 111 ⁇ plane is the most proximal plane and chemically stable plane. Therefore, the ⁇ 111 ⁇ plane is the slowest etch rate for aqueous sodium hydroxide solution. As a result, anisotropic etching occurs along the ⁇ 111 ⁇ plane of the silicon substrate after etching. As a result, on the silicon substrate, a texture having a depth of 0.1 to 10 ⁇ m was uniformly formed on the entire surface.
  • the tandem solar cell according to the first embodiment of the present invention differs from the tandem solar cell according to the second embodiment in that tunneling layers 112-1 and 112-1 are formed on the first and second surfaces of the crystalline silicon substrate 111, 113-1 may be formed. At this time, the tunnel layers 112-1 and 113-1 may be formed first on the second surface of the crystalline silicon substrate 111, and then on the first surface. Alternatively, the tunnel layers 112-1 and 113-1 may be formed on the first and second surfaces of the crystalline silicon substrate 111 at the same time.
  • the tunnel layers 112-1 and 113-1 may be deposited by a commonly used PECVD method. Particularly, when the tunnel layers 112-1 and 113-1 are sequentially formed on the first and second surfaces of the crystalline silicon substrate 111, a PECVD method or a thermal oxidation method can be used .
  • the PECVD process is widely used in the field of devices using silicon because of its ability to form films at relatively low process temperatures and high productivity.
  • CVD process is frequently performed in a low pressure region.
  • the deposition rate is decreased, and as a result, the productivity is lowered.
  • the thermal oxidation method is a method of exposing the silicon under a controlled atmosphere at a high temperature, thereby forming a high-temperature SiO 2 oxide layer.
  • the atmosphere uses water vapor or molecular oxygen as the oxidizing agent, which is also referred to as wet or dry oxidation.
  • the thermal oxidation method has a high productivity because it is performed by receiving a silicon substrate in a furnace at a high temperature in a boat and performing heat treatment.
  • Particularly wet oxidation is preferable to dry oxidation. This is because the wet oxidation is more advantageous in forming a thick oxide film than the dry oxidation, and further, the oxide film growth rate is higher.
  • layer deposition method is more preferable.
  • the ALD method has a disadvantage in that the productivity is generally lower than that of the CVD method, the ALD method has advantages of being excellent enough to overcome such disadvantages.
  • the ALD method can form a mono layer of a certain thickness for each supply period regardless of the shape of the substrate surface. More specifically, the ALD method includes: a step of injecting a source gas and adsorbing the source gas onto a substrate; Purging the residual gas and the unreacted gas with a purge gas; Injecting and depositing a reactive gas; And a process of purging the residual gas and the unreacted gas with a purge gas, and repeating the deposition of the monolayer until a thin film is formed to a predetermined thickness (see also Fig.
  • the growth rate of the film in the ALD process is proportional only to the number of feed cycles, not time, and does not depend largely on process conditions such as feed rate and flow rate.
  • the ALD method can precisely control the thickness of a thin film compared with other methods.
  • the deposition is carried out by using the adsorption in the atomic layer unit, and the unreacted gas is removed by the purge. Therefore, the ALD method can form a film having a uniform thickness even when the substrate area is wide, It is possible.
  • the reactive atomic layer deposited on the substrate from the gas phase can be stably deposited on the substrate by being bonded to the substrate by adsorption to the substrate. Therefore, the ALD method is advantageous in that a film having a uniform thickness is formed even in a powder or a porous material regardless of the irregularities of the substrate.
  • Another reason for using the ALD method in the present invention is that the low deposition rate of the ALD method can be improved by utilizing the deposition characteristic inherent to the ALD method.
  • a step of injecting a source gas and adsorbing the source gas to the substrate Purging the residual gas and the unreacted gas with a purge gas; Injecting and depositing a reactive gas; And purging the residual gas and the unreacted gas with the purge gas.
  • the deposition process in the ALD method is performed only by adsorption of the substrate and the source gas on the substrate surface and reaction of the source gas and the reaction gas on the substrate surface. Therefore, the deposition can be performed not only on one side but also on both sides of the substrate.
  • the traveling wave type reactor is easier to deposit on both planes of the substrate through the design change of the chuck of the substrate.
  • SiO 2 as the tunnel layers 112-1 and 113-1 was deposited by the ALD method by the following procedure.
  • tris (dimethylamino) silane (TDMAS), N, N-dimethylamino, trimethylsilane and tetrakis (dimethylamino) silane may be used as the silicon precursor, but the most effective precursor is tris (dimethylamino) silane .
  • H 2 O, H 2 O 2 , and ozone are theoretically possible as oxidants, but H 2 O is easy to remove surface SiH species generated by tris (dimethylamino) silane (TDMAS) Ozone was the most preferred.
  • the ALD deposition temperature was in the range of 150 ⁇ 550 °C.
  • the deposition temperature is directly proportional to the deposition rate, and the deposition rate is measured to increase as the deposition temperature increases.
  • 1 to 2 nm which is the thickness of the tunnel layers 112-1 and 113-1 applied in the present invention, a sufficient thickness can be secured by only about 20 to 40 ALD cycles.
  • the solar cells of the first embodiment and the second embodiment of the present invention all include the first conductivity type layers 113-2 and 113 and the second conductivity type layers 112-2 and 112 in common.
  • a second metal compound layer 112 having a second conductivity type is formed on the second surface of the crystalline silicon substrate 111.
  • the second metal compound layer 112 may be formed only on the second surface of the crystalline silicon substrate 111 or may be formed on the first surface and the second surface of the crystalline silicon substrate 111, The second metal compound layer 112 'formed on the first surface may be removed through a subsequent process.
  • the second conductive type layer 112 formed on the crystalline silicon substrate 111 according to the present invention may have a conductivity type opposite to that of the silicon substrate and may have the same conductivity type as the conductive type of the silicon substrate.
  • the second metal compound layer 112 may be deposited by a commonly used PECVD method, but the ALD (atomic layer deposition) method is more preferable in the present invention.
  • the second metal compound layer 112 formed on the crystalline silicon substrate 111 according to the present invention may have a conductivity type opposite to that of the silicon substrate and may have the same conductivity type as that of the silicon substrate.
  • the second metal compound layer 112 is a metal compound layer that can function as a p-type hole transport layer
  • the first metal compound layer 113 is an n- It is a metal compound layer that can act as a transport layer.
  • the second metal compound layer 112 is a metal compound layer that can serve as an n-type electron transporting layer
  • the first metal compound layer 113 is a p- And becomes a metal compound layer which can act as a hole transport layer.
  • the second metal oxide layer 112 may be a metal compound layer that can function as an n-type electron transporting layer
  • the first metal compound layer 113 may be a p- It may be a metal compound layer which can act as a hole transport layer.
  • a metal oxide of a MoOx component is deposited as a p-type metal compound in the present invention.
  • (NtBu) 2 (NMe 2 ) 2 Mo was used as an evaporation source of MoO x , and a metal source was implanted under conditions of a flow rate of 50 sccm and a feeding time of 1 second. N 2 gas was then purged under conditions of a flow rate of 500 sccm and a feeding time of 5 seconds. Then, ozone (O 3 ) was used as a reaction gas, and a MoO x metal oxide was deposited by reacting under conditions of a flow rate of 50 sccm and a feeding time of 1 second.
  • a thin film having a desired thickness was produced by setting such pulses as a basic one cycle and controlling the number of cycles.
  • the metal oxide of the TiO 2 component is deposited as an n-type metal compound in the present invention.
  • TTIP titanium isopropoxide
  • a metal source was implanted under conditions of a flow rate of 50 sccm and a feeding time of 1 second.
  • N 2 gas was then purged under conditions of a flow rate of 500 sccm and a feeding time of 5 seconds.
  • ozone (O 3 ) was used as a reaction gas, and a TiO 2 metal oxide was deposited by reacting under conditions of a flow rate of 50 sccm and a feeding time of 1 second.
  • the remaining residual gas and unreacted gas were then purged with N 2 gas under conditions of a flow rate of 500 sccm and a feeding time of 5 seconds.
  • a thin film having a desired thickness was produced by setting such pulses as a basic one cycle and controlling the number of cycles.
  • a conductive material transparent to the intermediate layer 114 is deposited on the second metal compound layer 112 having the second conductivity type (FIG. 8).
  • a transparent electrode or an intermediate layer 114 is formed on the substrate by a commonly known sputtering method, more specifically, RF magnetron sputtering.
  • FTO Fluorine Tin Oxide
  • AZO Alkyne-O-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-dilicates, but it is not necessarily limited to the above materials.
  • various transparent conductive oxides, metallic materials, and conductive polymers may also be used.
  • the second metal compound layer 112 'formed on the first surface of the crystalline silicon substrate 111 is removed through etching.
  • RIE reactive ion etching
  • a mixed gas of SF 6 and O 2 (SF 6 / O 2 ) or SF 6 and O 2 and Cl 2 (SF 6 / Cl 2 / O 2 ) is injected into the process chamber.
  • Plasma ions based on the source gas are generated in the spaces between the two electrodes when electric power of a corresponding magnitude is applied to two electrodes (not shown) provided between the substrates, and the etching operation by the generated plasma ions, that is, dry etching An operation is performed.
  • the magnitude of the electric power applied to the electrode may be about 3000 W / m2 to 6000 W / m2.
  • a first conductive type first metal compound layer 113 and a first conductive type charge injection layer (hereinafter, referred to as " first conductive type ") 113 having a first conductive type are formed on the lower portion of the crystalline silicon substrate 111 and the intermediate layer 114, 121) are formed (Fig. 10).
  • the first metal compound layer 113 and the first conductive type charge transporting layer 121 may be formed at the same time.
  • the process of manufacturing each unit layer of the tandem solar cell can be integrated or simplified.
  • the manufacturing method of the tandem solar cell according to the present invention not only can reduce the amount of expensive deposition equipment, but also omits the unit process, thereby reducing the lead time and the total process time (tact time, tact time.
  • the manufacturing method of the tandem solar cell according to the present invention can substantially improve the stability of the manufacturing process of the tandem solar cell by omitting a part of the deposition process having inherently very sensitive characteristics.
  • the first metal compound layer 113 and the first conductive type charge transport layer 121 having the first conductivity type are formed in the same manner as the second metal compound layer 112 having the second conductivity type described above, .
  • the first metal compound layer 113 and the first conductivity type charge transporting layer 121 may be a metal compound layer capable of acting as an n-type electron transporting layer .
  • Such a laminated structure corresponds to a normal tandem solar cell.
  • the metal compound layer which can act as the n-type electron transporting layer is one or two or more selected from TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , Al 2 O 3 and MgO / TiO 2 .
  • the first metal compound layer 113 and the first conductive-type charge-transporting layer 121 are formed of a metal compound layer capable of acting as a p- do.
  • Such a laminated structure corresponds to an inverted tandem solar cell.
  • the metal compound layer which can function as the p-type electron transporting layer is preferably one or two or more selected from MoO x , NiO, WO 3 , CuSCN, CuI, CuO, Cu 2 O and VO x .
  • the atomic layer deposition (ALD) method is used to simultaneously form the first metal compound layer 113 having the first conductivity type and the first conductivity type charge transporting layer 121.
  • ALD atomic layer deposition
  • the deposition process is performed only by the adsorption of the substrate and the source gas on the substrate and the reaction of the source gas and the reactive gas on the substrate, thereby enabling deposition on both sides of the substrate as well as on both sides.
  • the design of the chuck of the substrate facilitates deposition on both planes of the substrate.
  • the deposition conditions of the first metal compound layer 113 and the first conduction type charge transport layer 121 in the present invention are the same as the deposition conditions of the second metal compound layer 112 described above, and thus the description thereof will be omitted.
  • the transparent electrode layer 115 of the first electrode 140 is formed.
  • a transparent conductive oxide such as ITO (Indium Tin Oxide), ZITO (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide)
  • the transparent electrode layer 115 is formed of the intermediate layer 114 ) ≪ / RTI >
  • the grid electrode 116 may be directly formed on the second metal compound layer 113 without forming the transparent electrode layer 115, but the first metal compound layer 113 may be formed of a carrier rather than the transparent electrode layer 115. Since the mobility is lower, it is more preferable to form the transparent electrode layer 115 in terms of carrier mobility.
  • a grid electrode 116 is formed. If the grid electrode 116 is fabricated using a first electrode paste that includes inorganic particles such as metal particles and binders as well as inorganic particles that require high temperature for melting such as glass frit, It is preferable to form the perovskite absorption layer 122 before the perovskite absorption layer 122 is formed. This is because the perovskite absorption layer 122 is vulnerable to a high temperature so that when the perovskite absorption layer 122 is formed and then the grid electrode 116 of the first electrode 140 is formed at a high temperature, This is because the skew absorbing layer 122 is deteriorated.
  • the grid electrode 116 of the first electrode 140 can be manufactured by selectively applying the first electrode paste not including the glass frit, followed by low-temperature firing at the formation temperature of the first electrode 140 have.
  • the paste for the grid electrode 116 may include metal particles and an organic substance as a binder for low-temperature firing, and the glass frit is not included in the paste for the grid electrode 116.
  • the first electrode 140 may be formed at a temperature of 250 ° C or less, more specifically, 100-200 ° C.
  • the grid electrode 116 of the first electrode 140 may be formed before the second electrode 130, which will be described later, Can be formed in the same step. If the grid electrode 116 of the first electrode 140 is formed like the grid electrode 126 of the second electrode 130, the number of processes is reduced, which is more advantageous in terms of productivity.
  • the grid electrode 116 of the first electrode 140 of the present invention can be manufactured by using a printing method, an ink jet method, a photolithography method using a PR (photo-resist), or the like.
  • a perovskite absorption layer 122 is formed on the first conductive type charge transport layer 121 12).
  • the material of the perovskite absorption layer 122 in the present invention there can be used all so-called MA (Methylamminium) or FA (Formamidinium) perovskite compounds which are currently widely used.
  • MA Metalamminium
  • FA Formamidinium
  • a thin film process can be applied in addition to a conventional solution process.
  • the conventional solution process referred to in the present invention refers to processes such as ink-jet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting and slot-die coating of the perovskite absorption layer.
  • the solution process is advantageous in that it can form an optical absorber constituting a photoactive layer through an extremely simple, easy and inexpensive process of applying and drying a solution.
  • the coating solution is spontaneously crystallized by drying to enable formation of a coarse crystal grain-like light absorber.
  • it has an advantage of excellent conductivity for both electrons and holes.
  • an inorganic layer is first coated on the first conductive type charge transport layer 121.
  • the inorganic layer in the present invention was prepared by the solution method using PbI 2 .
  • PbI 2 solution was prepared by dissolving 4 mmol of PbI 2 (Sigma-Aldrich, 99%) in 4 ml of N, N-dimethylformamide (DMF) (Sigma-Aldrich, 99.8%).
  • 40 ml of the PbI 2 solution was coated on the substrate having the first conductive type charge transport layer 121 formed thereon by spin coating at a speed of 500 to 5,000 rpm for 30 seconds to coat the inorganic layer.
  • the substrate coated with the inorganic layer was dried at 100 DEG C for 15 minutes.
  • a substrate formed of the inorganic layer is in 2-propanol (Sigma-Aldrich, 99.5%) 0.01g / ml (CH (NH 2) 2) Br was immersed in an organic solution and then 100 °C was rotated for 30 seconds at maximum 3,000rpm Lt; / RTI > for 15 minutes.
  • the perovskite absorption layer 122 in the present invention is formed by physical vapor deposition or chemical vapor deposition using sputtering, electron beam, or the like in addition to the solution process.
  • the perovskite absorption layer may be formed by a single step deposition or a sequential step deposition. However, since a single step is difficult to produce a uniform thin film shape, a sequential step is more preferable.
  • a post-heat treatment process is performed in the present invention.
  • the post-heat treatment process is performed within a temperature range of room temperature to 200 ° C within about 3 hours. There is no particular limitation on the lower limit of the post-treatment temperature, but if the temperature is higher than 200 ° C, the perovskite-absorbing polymer material may thermally degrade.
  • the precursor layers may react with each other to cause pyrolysis of the respective precursor layers or compositional change due to pyrolysis before forming the perovskite layer.
  • a second conductive type charge transport layer 123 is formed on the perovskite absorption layer 122.
  • the first conductive type charge transport layer 121 is an n-type electron transport layer
  • a p-type hole transport layer is formed as the second conductive type charge transport layer 123, And corresponds to a perovskite tandem solar cell having a normal laminated structure.
  • the first conductive type charge transport layer 121 is a p-type hole transport layer
  • an n-type electron transport layer is formed in the second conductive type charge transport layer 123, which corresponds to a perovskite tandem solar cell having an inverted laminated structure.
  • Spiro-OMeTAD is typically used as a material for the p-type second conductivity type charge transporting layer 123.
  • HTM hole transport layer
  • C 60 is typically used as the material of the n-type second conductivity type charge transport layer 123.
  • the conventional solution method is used as one embodiment for forming the n-type second conductivity type charge transporting layer 123.
  • the fullerene derivative is dissolved in a solvent 10-30 seconds Spin coating containing C 60 and maintained for 1 ⁇ 3 hours at room temperature, the electron transport layer was formed.
  • a front transparent electrode 125 for the second electrode 130 is formed in the present invention (FIG. 14).
  • the transparent electrode layer 125 is formed on the entire upper surface of the perovskite solar cell 120 to collect the charge generated in the perovskite solar cell 120.
  • the transparent electrode layer 125 may be formed of various transparent conductive materials. The same material as the transparent conductive material of the intermediate layer 114 may be used as the transparent conductive material.
  • the grid electrode 126 of the second electrode 130 is disposed on the front transparent electrode layer 125 and is disposed in a part of the transparent electrode layer 125.
  • the grid electrode 126 of the second electrode 130 may be manufactured by selectively applying a first electrode paste not containing glass frit and then low-temperature firing at a second temperature.
  • the second electrode paste may include metal particles and an organic material that is a binder for low-temperature firing, and the second electrode paste does not include glass frit.
  • the second temperature may be 250 ° C or less, more specifically 100 to 200 ° C.

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  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne une cellule solaire dans laquelle certaines des couches unitaires constituant la cellule solaire sont formées simultanément de manière à améliorer le facteur de transmission lumineuse et à supprimer une fuite de courant, au moyen d'une technologie de jonction tunnel, ce qui permet à la cellule solaire de présenter d'excellentes caractéristiques de température et un excellent rendement de conversion photoélectrique, ou des matériaux des couches unitaires constituant la cellule solaire sont conçus de manière à maximiser le rendement de conversion photoélectrique par adaptation de courant entre cellules solaires.
PCT/KR2018/009356 2017-09-05 2018-08-14 Cellule solaire et son procédé de fabrication Ceased WO2019050185A1 (fr)

Applications Claiming Priority (4)

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KR1020170113463A KR102541127B1 (ko) 2017-09-05 2017-09-05 텐덤 태양전지 및 그 제조 방법
KR10-2017-0113463 2017-09-05
KR1020170134041A KR102600452B1 (ko) 2017-10-16 2017-10-16 태양전지
KR10-2017-0134041 2017-10-16

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CN113257940A (zh) * 2020-02-13 2021-08-13 隆基绿能科技股份有限公司 叠层光伏器件及生产方法
CN115000191A (zh) * 2022-06-05 2022-09-02 北京工业大学 一种新型氧化硅复合钝化层化合物异质结接触硅太阳电池
WO2023097365A1 (fr) * 2021-12-01 2023-06-08 Australian National University Cellule photovoltaïque en tandem
EP4117044A4 (fr) * 2020-03-04 2023-11-22 Shangrao Jinko solar Technology Development Co., LTD Cellule solaire et son procédé de fabrication
AU2020437211B2 (en) * 2020-03-27 2024-05-23 Longi Green Energy Technology Co., Ltd. Stacked photovoltaic device and production method
EP4456156A1 (fr) * 2023-04-25 2024-10-30 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Cellule solaire tandem et son procédé de fabrication

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CN113257940A (zh) * 2020-02-13 2021-08-13 隆基绿能科技股份有限公司 叠层光伏器件及生产方法
EP4106021A4 (fr) * 2020-02-13 2023-08-02 Longi Green Energy Technology Co., Ltd. Dispositif photovoltaïque en tandem et procédè de production
CN113257940B (zh) * 2020-02-13 2023-12-29 隆基绿能科技股份有限公司 叠层光伏器件及生产方法
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EP4117044A4 (fr) * 2020-03-04 2023-11-22 Shangrao Jinko solar Technology Development Co., LTD Cellule solaire et son procédé de fabrication
AU2020437211B2 (en) * 2020-03-27 2024-05-23 Longi Green Energy Technology Co., Ltd. Stacked photovoltaic device and production method
US12142704B2 (en) 2020-03-27 2024-11-12 Longi Green Energy Technology Co., Ltd. Tandem photovoltaic device and production method
WO2023097365A1 (fr) * 2021-12-01 2023-06-08 Australian National University Cellule photovoltaïque en tandem
CN115000191A (zh) * 2022-06-05 2022-09-02 北京工业大学 一种新型氧化硅复合钝化层化合物异质结接触硅太阳电池
EP4456156A1 (fr) * 2023-04-25 2024-10-30 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Cellule solaire tandem et son procédé de fabrication
WO2024225901A1 (fr) * 2023-04-25 2024-10-31 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Cellule solaire tandem et son procédé de fabrication

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